Paint for Detection of Radiological or Chemical Agents

ABSTRACT

A paint that warns of radiological or chemical substances comprising a paint operatively connected to the surface, an indicator material carried by the paint that provides an indication of the radiological or chemical substances, and a thermo-activation material carried by the paint. In one embodiment, a method of warning of radiological or chemical substances comprising the steps of painting a surface with an indicator material, and monitoring the surface for indications of the radiological or chemical substances. In another embodiment, a paint is operatively connected to a vehicle and an indicator material is carried by the paint that provides an indication of the radiological or chemical substances.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of application Ser. No. 11/293,657filed Dec. 1, 2005, entitled “Paint for Detection of radiological orChemical Agents”. This application claims the benefit of U.S.Provisional Patent Application No. 60/712,006 filed Aug. 26, 2005 byJoseph C. Farmer, James Brunk, and S. Daniel Day; titled “Smart Surface& Intellicoat—Coatings for Detection of Radiation-Differential andIntegrating Coatings” are incorporated herein by this reference.

Related inventions are disclosed and claimed in the following co-pendingapplication: U.S. patent application Ser. No. 11/293,675, filed Dec. 1,2005, by Joseph C. Farmer, titled “Paint for Detection of Corrosion andWarning of Chemical and Radiological Attack,” which is incorporatedherein by reference.

STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSOREDRESEARCH AND DEVELOPMENT

The United States Government has rights in this invention pursuant toContract No. DE-AC52-07NA27344 between the United States Department ofEnergy and Lawrence Livermore National Security, LLC for the operationof Lawrence Livermore National Laboratory.

BACKGROUND

1. Field of Endeavor

The present invention relates to detection and more particularly topaint for detection of radiological and chemical materials.

2. State of Technology

Paints/coatings of the present invention enable the detection ofradiological and chemical warfare agents through direct orinstrument-assisted visual inspection. Such paints and coatings can warnsoldiers of radiological and chemical attack. This feature can be addedto tactical vehicles during maintenance operations. The use of paintsinside buildings, trains, and subway tunnels would provide a means ofdetecting the presence of radiological and chemical warfare agents overlarge surfaces.

Radiological warfare agents include radiological bombs, dirty bombs, andother systems for releasing radioactive material. Current concerns aboutradiological warfare tend to be focused on bombs and on deliberatepollution of air, water, or ground. Some radiological agents, such asplutonium, are extremely virulent, and can kill over time withnear-certainty at doses as low as one microgram. However, being anextremely heavy metal, and extremely dangerous and difficult to grind topowder, it seems unlikely that it would be an effective means of suchwarfare. It is more likely that lighter elements might be used, thoseisotopes that are very unstable and may be created just in time for use.It is therefore believed that the existing regimes of inspection of labsand other facilities handling radioactive material, if strictlyenforced, can effectively prevent their use to kill in a systematic anddeliberate manner. For these reasons, some experts consider radiologicalwarfare to have the same problems as chemical warfare agents.

Nerve agents are potent cholinesterase-inhibiting organophosphorouscompounds. Symptoms of muscarinic and nicotinic overstimulation includeabdominal pain, vomiting, diarrhea, excessive salivation and sweating,bronchospasm, copious pulmonary secretions, muscle fasciculations andweakness, and respiratory arrest. Seizures, bradycardia, or tachy-cardiamay be present. Severe dehydration can result from volume loss due tosweating, vomiting, and diarrhea. Sequelae can include polyneuropathyand neuropsychiatric changes.

U.S. Pat. No. 5,935,862 to Thaddeus J. Novak issued Aug. 10, 1999 formicrospot test methods and a field test kit for on-site inspections ofchemical agents provides the following state of technology information:“Over the years, various highly toxic chemical warfare agents (CWA's)have been developed and stockpiled by several nations. In view of thebiological hazards associated with CWA's and degradation productsthereof, chemical warfare conventions (CWC's) have been developed bycertain countries. These CWC's monitor, identify and, if necessary,dispose of CWA's which are not in compliance with the convention. As aresult of the convention, it is often necessary to conduct inspectionsof various sites in order to assure compliance . . . . In view of theadvantages of rapidly and accurately identifying the presence of CWA'sand associated by-products, and further in view of the need to addressthe shortcomings associated with currently available detection methods,there is still a need for new and improved detection methods and kits.”

SUMMARY

Features and advantages of the present invention will become apparentfrom the following description. Applicants are providing thisdescription, which includes drawings and examples of specificembodiments, to give a broad representation of the invention. Variouschanges and modifications within the spirit and scope of the inventionwill become apparent to those skilled in the art from this descriptionand by practice of the invention. The scope of the invention is notintended to be limited to the particular forms disclosed and theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

The present invention provides a paint that warns of radiological orchemical substances comprising a paint operatively connected to thesurface, an indicator material carried by the paint that provides anindication of the radiological or chemical substances, and athermo-activation material carried by the paint. In one embodiment thepresent invention provides a method of warning of radiological orchemical substances comprising the steps of painting a surface with anindicator material, and monitoring the surface for indications of theradiological or chemical substances. In another embodiment the presentinvention provides a system that warns of radiological or chemicalsubstances comprising a vehicle, a paint operatively connected to thevehicle, an indicator material carried by the paint that provides anindication of the radiological or chemical substances, and athermo-activation material carried by the paint.

The invention is susceptible to modifications and alternative forms.Specific embodiments are shown by way of example. It is to be understoodthat the invention is not limited to the particular forms disclosed. Theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated into and constitute apart of the specification, illustrate specific embodiments of theinvention and, together with the general description of the inventiongiven above, and the detailed description of the specific embodiments,serve to explain the principles of the invention.

FIG. 1 illustrates a system that provides a warning of radiologicalwarfare agents.

FIG. 2 illustrates another embodiment of a system of the presentinvention.

FIG. 3 illustrates yet another embodiment of a system of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

Referring to the drawings, to the following detailed description, and toincorporated materials, detailed information about the invention isprovided including the description of specific embodiments. The detaileddescription serves to explain the principles of the invention. Theinvention is susceptible to modifications and alternative forms. Theinvention is not limited to the particular forms disclosed. Theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

Referring to the drawings embodiments of systems of the presentinvention are illustrated. The systems provide warning of radiologicaland chemical warfare agents. The systems comprise painting a surface ofa relevant structure with indicator paint and monitoring the paint forindications of the radiological or chemical warfare agents. The paint103 contains material that causes the paint to provide an indication ofthe chemical or radiological warfare agents.

Radiological Warfare Agents (RWAs) are detected through scintillation.Special crystalline pigments are added to the paint that produceluminescence when irradiated by alpha, beta, or gamma rays. Theluminescence is used to stimulate florescence in dyes within thepolymeric binder of the paint.

In Chemical Warfare Agents (CWA) detection, an alkyloxy methylphosphonicacid in the paint is reacted with an appropriate dehydrating agent toproduce cholinesterase inhibitor. The cholinesterase inhibitor is thendetected with a pH-sensitive, chromogenic indicator molecule.

Referring to the drawings and in particular to FIG. 1, an embodiment ofa system of the present invention is illustrated. This embodiment isdesignated generally by the reference numeral 100. The system 100provides a warning of radiological warfare agents. The system 100 forwarning of radiological warfare agents comprises painting a surface 102of a relevant structure 101 with an indicator paint 103 and monitoringthe paint 103 for indications of the radiological or chemical warfareagents. The Radiological Warfare Agents (RWA) are illustrated by thecloud 109 in FIG. 1. The RWA could also be from a source of radiationsuch as a nuclear weapon. Also the radiation could come from a sourcesuch as a nuclear reactor.

The paint 103 contains material that causes the paint to provide anindication of the RWA or other source of radiation. The radiation isdetected through scintillation. Special crystalline pigments are addedto the paint that produce luminescence when irradiated by alpha, beta,or gamma rays. The luminescence is then be used to stimulate florescencein dyes within the polymeric binder of the paint.

Referring again to FIG. 1, the detection of RWA or other radiation bythe paint 103 will be described in greater detail. The system 100utilizes the inclusion of scintillation agents into the paint 103.Special pigments 105, 106, and 107, are added to the paint 103 thatproduce scintillation and luminescence λ₁, λ₂, and λ₃ when irradiated byalpha (α), beta (β), and gamma (γ) rays 104. The pigments 105, 106, and107 are contained in an optically transparent organic binder 112. Alphascintillation pigments 105 produce the luminescence λ₁, Betascintillation pigments 106 produce the luminescence λ₂. Gammascintillation pigments 107 produce the luminescence λ₃. Thescintillation is used to stimulate florescence thermal luminescentpigments 108 that are incorporated within the optically transparentorganic binder 112 of the paint 103. The laser 110 directs a thermalpulse 111 onto the paint 103 that stimulates the scintillations.

These scintillations are detected by detector 113. For example, thesescintillations can be detected directly with a photomultiplier tube(PMT) coupled with an amplifier and pulse-counting electronics, digitalCCD-array cameras, or other such devices, or used to stimulateflorescence in dyes within the polymeric binder 112 of the paint 103with detection of the secondary emission. Some of the components thatcan be used in the system 100 are: (1) Inorganic Scintillators, such asLiI (Sn) for neutron detection, ZnS (Ag) for α detection, NaI (Tl) for γdetection, CsI (Tl) for γ detection, CsI (Na) for γ detection, BGO for γdetection, and BaF₂ for γ detection; and (2) Organic Scintillators, suchas anthracene for β and neutron detection, trans-stilibene for βdetection, p-terphenyl for β detection, diphenyloxazole for β andneutron detection, tetraphenyl butadiene for β detection, and terphenylin polystyrene for β detection. These are incorporated into the paint103, thereby imparting radiation sensitivity. It is to be understoodthat other active agents can also be used.

Applicant has successfully demonstrated radiation-sensitive paints ofthe present invention illustrated in FIG. 1. This has been accomplishedwith the successful detection of scintillations from painted surfacesirradiated by both alpha particles and gamma rays. Alpha particles froma weak 1-nCi plutonium-239 source were detected with a specialscintillation paint formulation, a photomultiplier tube (PMT), and anappropriate pulse counting network. Parametric studies were performed,determining the scintillation rate as a function of coating thickness,and distance of separation between the coating and source. An optimumpaint thickness was identified for this scenario. It was found that thepaint has to be thick enough to provide an easily detectable level ofscintillation, but not so thick that the scintillations undergoself-absorption by the paint before reaching the detector. Gamma raysfrom a 100-μCi radium-226 source were also detected with another specialscintillation paint formulation, by performing time-lapse photographywith a commercially available 12.8-megapixel camera.

The paint illustrated by the system 100 illustrated in FIG. 1 can beapplied using various application techniques. For example, numerousmethodologies can be used for the production of derivative-type paintsand coatings for detecting the presence of radiological agents on ornear surfaces, and for the production of “integrating” paints andcoatings for quantifying long-term exposure to doses of radiation. Thesecoatings incorporate scintillation and/or thermo-luminescent materialsas pigments and can be easily produced with a variety of processesincluding, organic polymeric binders, spray-on paints or coatings withorganic polymeric binders, brush-on paints or coatings with organicpolymeric binders, coatings and films produced with web coater andorganic polymeric binders, powder coatings, inorganic ceramic/metallicbinders, cold-spray processes, and thermal-spray processes.

The paints and coatings can be interrogated by any one of numeroussystems. These include, but are not limited: (1) instantaneous detectionof alpha-, beta- or gamma-induced scintillations from pigment particleswith a PMT coupled to an amplifier and pulse-counting electronics, adigital CCD-array camera, or other such devices, for derivative-typecoatings; or (2) laser-pulse, filament, or localized-microwave heatingto induce photon emission from irradiated thereto-luminescent pigmentparticles, followed by detection with a PMT coupled to an amplifier andpulse-counting electronics, a digital CCD-array camera, or other suchdevices, for integral-type coatings, which integrate flux over theexposure time to provide a signal proportional to dose.

The present invention illustrated by the system 100 illustrated in FIG.1 has may uses. For example radiation-sensitive paints and coatings canbe used to monitor exposure in various scenarios of interest: (1) aspaints for buildings and equipment in industrial plants involved in theproduction of nuclear and radiological materials; (2) as paints for theinside of nuclear power plants, nuclear powered ships, and submarines;(3) as paints for trucks and shipping containers and road-sidefacilities along shipping routes; (4) as paints for unmanned aerialvehicles, micro airships, and other surveillance devices; and (5) aspaints for the detection and monitoring of activities involvingradiological materials. In addition to enabling the long-term exposure(dose) of operating personnel in nuclear plants and nuclear-poweredships to be monitored, surfaces coated with these paints can be used totrack and image the spread of radioactive contamination. Ultimately,thermo-luminescent paints and coatings could be used as a basis forqualifying the receipt of shipping containers for acceptance into theUnited States, where such qualification could be done through fieldinterrogation of the painted surface, or through quantification ofsampled paint chips.

Referring now to FIG. 2, another embodiment of a system of the presentinvention is illustrated. This embodiment of the system is designatedgenerally by the reference numeral 200. The system 200 provides awarning of chemical warfare agents. The Chemical Warfare Agents (CWA)are illustrated by the cloud 208. The system 200 for warning of chemicalwarfare agents comprises painting a surface 202 of a relevant structure201 with an indicator paint 203 and monitoring the paint 203 forindications of the chemical warfare agents. The paint 203 containsmaterial that causes the paint to provide an indication of the chemicalwarfare agents. In one embodiment of the system 200, Chemical WarfareAgents (CWA) detection, an alkyloxy methylphosphonic acid in the paint204 is reacted with an appropriate dehydrating agent to producecholinesterase inhibitor. The cholinesterase inhibitor is then detectedwith a pH-sensitive, chromogenic indicator molecule. In specificembodiments, the indicator paint 203 is further developed to enable doserecording due to any historic exposure to radiation. This second classof paint or coating, referred to here as an integrating paint orcoating, depends upon thermal luminescence as a means of recordingaccumulated dose. In this case, an inorganic pigment (thermalluminescent material) produces luminescence proportional to radiationexposure (dose) during post-exposure heating.

Referring again to FIG. 2, the detection of Chemical Warfare Agents(CWA) by the paint 203 will be described in greater detail. For examplethe cloud 208 can include nerve agents that are potentcholinesterase-inhibiting organophosphorous compounds. Symptoms ofmuscarinic and nicotinic overstimulation include abdominal pain,vomiting, diarrhea, excessive salivation and sweating, bronchospasm,copious pulmonary secretions, muscle fasciculations and weakness, andrespiratory arrest. Seizures, bradycardia, or tachy-cardia may bepresent. Severe dehydration can result from volume loss due to sweating,vomiting, and diarrhea. Sequelae can include polyneuropathy andneuropsychiatric changes.

The system 200 imparts chemical sensitivity to the paint or coating 203to enable the detection of the CWA in the cloud 208. For example, U.S.Pat. No. 5,935,862 to Thaddeus J. Novak and U.S. Pat. No. 6,403,329 toThaddeus J. Novak et al describe an alkyloxy methylphosphonic acid thatis reacted with appropriate dehydrating agents to produce cholinesteraseinhibitor. U.S. Pat. No. 5,935,862 and U.S. Pat. No. 6,403,329 areincorporated herein by reference. The indicator paint 203 is furtherdeveloped to enable dose recording due to any historic exposure toradiation. This second class of paint or coating, referred to here as anintegrating paint or coating, depends upon thermal luminescence as ameans of recording accumulated dose. In this case, an inorganic pigment(thermal luminescent material) produces luminescence proportional toradiation exposure (dose) during post-exposure heating.

Some of the reagents involved used in the system 200 are: (1)Methylphosphonic Acid (MPA) & Alkyloxy Methylphosphonic Acids (AMPA),ethyl MPA (EMPA), isopropyl MPA (IMPA), cyclohexyl MPA (CMPA), pinacolylMPA (PMPA), O-ethyl methylphosphonothioic acid (EMPTA), and 1,4-dithiane(DITHIANE); (2) Esterification Reagents, dialkyl sulfate, and dialkyliodide; (3) Dehydrating & Other Reagents, 1,3-dicyclohexylcarbodiimideand 1,3-diisopropylcarbodiimide. (4) Chromogenic Detector Reagent,bromocresol green, 7,7,8,8-tetracyanoquinodimethane (TCNQ), and goldchloride with/without NaOH; and (5) Solid Absorbent, alumina and silica.The following specific examples are embodiments of the system 200:CaSO₄(Tu), Li₂B₄)7(Cu), and Al₂O₃.

The cholinesterase inhibitor, produced by reacting AMPA with anappropriate dehydrating agent, is then detected with a pH-sensitive,chromogenic indicator molecule. Bromocresol green is a commonchromogenic indicator, which is blue at pH 5.4, and yellow at3.8<pH<5.4. The presence of cholinesterase inhibitor at the surface ofthe solid absorbent material lowers the pH from above 5.4 to an acidiclevel between 3.8 and 5.4, thereby producing a color change.

The system 200 for detection of chemical warfare agents utilizes theincorporation of the esterification and dehydration reagents into thecoating 205 in a way to maintain their activity. This includes directincorporation the functionality into the polymeric coating, triggeredrelease of the reagents from capsules, and transport-limitedtime-release.

The paints and coatings can be interrogated by any one of numeroussystems. These include, but are not limited: (1) instantaneous detectionof alpha-, beta- or gamma-induced scintillations from pigment particleswith a PMT coupled to an amplifier and pulse-counting electronics, adigital CCD-array camera, or other such devices, for derivative-typecoatings; or (2) laser-pulse, filament, or localized-microwave heatingto induce photon emission from irradiated thermo-luminescent pigmentparticles, followed by detection with a PMT coupled to an amplifier andpulse-counting electronics, a digital CCD-array camera, or other suchdevices, for integral-type coatings, which integrate flux over theexposure time to provide a signal proportional to dose.

Referring again to the drawings and in particular to FIGS. 3A and 3B,another embodiment of a system of the present invention is illustrated.This embodiment of the system is designated generally by the referencenumeral 300. The system 300 provides a warning of radiological orchemical warfare agents encountered by an unmanned aerial vehicle (UAV)301. As previously described, the Radiological Warfare Agents (RWAs) aredetected through scintillation. Special crystalline pigments are addedto the paint that produce luminescence when irradiated by alpha, beta,or gamma rays. The luminescence can then be used to stimulateflorescence in dyes within the polymeric binder of the paint. Also, aspreviously described, the Chemical Warfare Agents (CWA) are detectedthrough use of an alkyloxy methylphosphonic acid in the paint that isreacted with an appropriate dehydrating agent to produce cholinesteraseinhibitor. The cholinesterase inhibitor is then detected with apH-sensitive, chromogenic indicator molecule.

The UAV 301 is equipped with a camera 306. The camera 306 is moveableand can train its line of sight 305 to various locations includingnumerous locations on the body of the UAV 301. As illustrated in FIG.3A, the camera line of sight 305 is trained on a viewing surface 303 onthe body of the UAV 301. The camera line of sight 305 can be trained onother portions of the body of the UAV 301. For example an alternateviewing surface 308 is shown on one of the rear stabilizers of the UAV301.

The UAV 301 is also equipped with a laser 307. The laser 307 is moveableand can train its laser beam 304 to various locations including numerouslocations on the body of the UAV 301. As illustrated in FIG. 3A, thelaser beam 304 is directed onto the viewing surface 303 on the body ofthe UAV 301. The laser beam 304 can be trained on other portions of thebody of the UAV 301. For example, the laser beam 304 can be trained onthe alternate viewing surface 308 shown on one of the rear stabilizersof the UAV 301.

Referring now to FIG. 3B, the viewing surface 303 is shown in greaterdetail. The viewing surface 303 includes two paint strips 309 and 310.

The paint strip 309 is a paint strip for chemical detection and thepaint strip 310 is a paint strip for radiation detection. The paintstrip 308 for chemical detection contains material that causes the paintto provide an indication of the chemical warfare agents.

Paint for chemical detection has been described previously in connectionwith FIG. 2 and that description is incorporated in this description ofthe paint strip 309 of the system 300. The paint strip 310 for radiationdetection contains material that causes the paint to provide anindication of the radiation warfare agents.

Paint for radiation detection has been described previously inconnection with FIG. 1 and that description is incorporated in thisdescription of the paint strip 310 of the system 300.

The two paint strips 309 and 310 are further developed to enable doserecording due to any historic exposure to radiation. This second classof paint or coating, referred to here as an integrating paint orcoating, depends upon thermal luminescence as a means of recordingaccumulated dose. In this case, an inorganic pigment (thermalluminescent material) produces luminescence proportional to radiationexposure (dose) during post-exposure heating. The laser 307 provides theheating of the paint strips 309 and 310 through the laser beam 304.

By monitoring the viewing area 303 with the camera 306, it is possibleto monitor whether the UAV 301 has encountered chemical warfare agentsor radiation warfare agents. Since UAVs are routinely equipped withcameras and the cameras and the cameras are moveable to view variousportions of the body of the UAV, the addition of the system 300 providesa warning of chemical or radiological warfare agents is a simple andcost effective system. The system 300 can be retrofitted to existingUAVs with a minimum of cost and time.

While the invention may be susceptible to various modifications andalternative forms, specific embodiments have been shown by way ofexample in the drawings and have been described in detail herein.However, it should be understood that the invention is not intended tobe limited to the particular forms disclosed. Rather, the invention isto cover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the invention as defined by the followingappended claims.

1. A paint on a surface that warns of radiological or chemical substances, comprising: a paint operatively connected to the surface, an indicator material carried by said paint that provides an indication of the radiological or chemical substances, and a thermo-activation material carried by said paint.
 2. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said thermo-activation material includes thermo-luminescent materials.
 3. The paint on a surface that warns of radiological or chemical substances of claim 2 wherein said indicator material is a material that provides an indication of the chemical substances.
 4. The paint on a surface that warns of radiological or chemical substances of claim 2 wherein said indicator material is a material that provides an indication of the radiological substances.
 5. The paint on a surface that warns of radiological or chemical substances of claim 2 wherein said indicator material includes scintillation materials.
 6. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes photo-luminescent pigments for imaging the movement of radioisotope tracers sensitive to migration of dissolved metal.
 7. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material is scintillation material.
 8. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes crystalline pigments that produce luminescence when irradiated by alpha, beta or gamma rays.
 9. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes crystalline pigments that produce luminescence when irradiated by alpha rays.
 10. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes crystalline pigments that produce luminescence when irradiated by beta rays.
 11. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes crystalline pigments that produce luminescence when irradiated by gamma rays.
 12. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes one or more materials sensitive to chemical agents, or nerve agents, or radiological agents.
 13. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes one or more materials sensitive to alpha-particle emitters, or beta-particle emitters, or gamma-ray emitters, or X-ray emissions.
 14. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes organic binders with transparency for the emitted photons.
 15. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes organic binders with refractive-index matching to the pigment particles, thereby minimizing signal loss due to scattering of emissions away from aperture of detector.
 16. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes inorganic scintillation pigments sensitive to alpha particles or gamma rays.
 17. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes organic scintillation pigments sensitive to beta particles.
 18. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said thermo-activation material includes thermo-luminescent pigments sensitive to alpha particles, beta particles or gamma rays.
 19. The paint on a surface that warns of radiological or chemical substances of claim 1 wherein said indicator material includes photo-luminescent pigments sensitive to alpha particles, beta particles or gamma rays. a system that warns of radiological or chemical substances of claim 20 wherein said thermo-activation material includes thermo-luminescent materials.
 20. A method of warning of radiological or chemical substances, comprising the steps of: painting a surface with an indicator material, and monitoring said surface for indications of the radiological or chemical substances.
 21. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes painting a surface with a thermal luminescent material.
 22. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material comprises painting a surface with scintillation material.
 23. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material comprises painting a surface with crystalline pigments that produce luminescence when irradiated by alpha, beta or gamma rays.
 24. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of synthesis and production of radiation-sensitive pigments including at least one of the growth of bulk crystals followed by milling in inert cryogen liquids or nucleation and precipitation from the gas phase or nucleation and precipitation from the liquid phase.
 25. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of dispersing pigments uniformly and homogeneously in paint solutions for application by brush or spray using surfactant or ultrasonics or agitation by gas sparging or impeller.
 26. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of applying organic-type paints or coatings with scintillation, thermo-luminescent or photoluminescent pigments including brushing, spraying, dipping, electrophoretic deposition, or electrochemical deposition.
 27. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of applying inorganic-type films or coatings with scintillation, thermo-luminescent or photo-luminescent materials including physical vapor deposition, including evaporation or magnetron sputtering or chemical vapor deposition or electrochemical deposition or cold spray particles suspended in high-velocity gas streams or thermal spray including flame spray, plasma spray, wire-arc, high-velocity oxy-fuel, or detonation gun processes.
 28. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of applying inorganic-type films or coatings with sensitivity to corrosion and environmental cracking, based upon sensitivity to pH, chloride, dissolved metal cations, electrochemical potential, oxidation state, stress and strain including physical vapor deposition or evaporation or magnetron sputtering or chemical vapor deposition or electrochemical deposition or cold spray particles suspended in high-velocity gas streams or thermal spray including flame spray, plasma spray, wire-arc, high-velocity oxy-fuel, or detonation gun processes.
 29. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of applying materials sensitive to chemical warfare agents as inorganic coatings with processes including physical vapor deposition including evaporation and magnetron sputtering, chemical vapor deposition, electrochemical deposition, cold spray particles suspended in high-velocity gas streams, or thermal spray including flame spray, plasma spray, wire-arc, high-velocity oxy-fuel, or detonation gun processes wherein said materials will be infiltrated with reagents that react with the chemical warfare agents to produce changes in pH that can be detected with colorimetric and ratiometric fluorescent indicators.
 30. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of applying materials sensitive to chemical warfare agents as inorganic coatings with processes including physical vapor deposition including evaporation and magnetron sputtering, chemical vapor deposition, electrochemical deposition, cold spray particles suspended in high-velocity gas streams, or thermal spray including flame spray, plasma spray, wire-arc, high-velocity oxy-fuel, or detonation gun processes wherein said materials will react to produce detectable changes in oxidation state, electrochemical potential or other coating characteristics.
 31. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of painting a surface with paints or coatings with multifunctional paints or coatings with multiple pigments or additives for simultaneous detection of various types of radiation, including alpha particles, beta particles or gamma rays.
 32. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of painting a surface with paints or coatings with multifunctional paints or coatings with multiple pigments or additives for simultaneous detection of various types of chemical warfare agents.
 33. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the step of painting a surface with paints or coatings with multifunctional paints or coatings with multiple pigments for the simultaneous detection of radiological agents, chemical agents or corrosion.
 34. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the use of functionalized porous pigments for the detection of infectious and biological warfare agents.
 35. The method of warning of radiological or chemical substances of claim 20 wherein said step of painting a surface with an indicator material includes the use of scintillation, thermo-luminescent, or photo-luminescent pigments engineered for energy discrimination of the detected alpha, beta or gamma particles including multiple types of thermo-luminescent pigments having a characteristic elemental composition observable in scanning electron microscope and have a characteristic emission wavelength or pigments can be coated with a shield material with each different type of pigment having different coating thickness wherein said coatings of different thickness serve to impart energy discrimination characteristics to the coated pigment particles.
 36. The method of warning of radiological or chemical substances of claim 20 including the step of a paint-chip sample taken and the organic matrix and shield coating dissolved wherein upon heating each pigment particle will release a pulse of photons at its characteristic wavelength with the detected photon pulses at each characteristic wavelength representing a particular band of radiation energy.
 37. The method of warning of radiological or chemical substances of claim 20 including the step of interrogating of derivative-type coatings with scintillation pigments, including embedded fiber optics, embedded photodiodes, stand-off optics with PMT with amplifier and pulse counting, or digital CCD-array camera with time-lapse exposure. 